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WO1993002046A1 - Procede de production de nitrile - Google Patents

Procede de production de nitrile Download PDF

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Publication number
WO1993002046A1
WO1993002046A1 PCT/JP1992/000928 JP9200928W WO9302046A1 WO 1993002046 A1 WO1993002046 A1 WO 1993002046A1 JP 9200928 W JP9200928 W JP 9200928W WO 9302046 A1 WO9302046 A1 WO 9302046A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
producing nitrile
aldoxime
reaction
reaction system
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1992/000928
Other languages
English (en)
Japanese (ja)
Inventor
Masayuki Oku
Yoshiaki Fujikura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to DE69206250T priority Critical patent/DE69206250T2/de
Priority to EP92915837A priority patent/EP0550762B1/fr
Publication of WO1993002046A1 publication Critical patent/WO1993002046A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles

Definitions

  • the present invention relates to a method for easily producing a nitrile useful as a raw material for organic synthesis of a fragrance, a fragrance, a pharmaceutical or the like in a low yield.
  • an object of the present invention is to provide a method for producing nitrile, which has a high yield and is extremely advantageous from the viewpoint of production economics.
  • the present invention relates to a hydroxide of an alkali metal, an alcoholate of an alkali metal, In the presence of one or more catalysts selected from earth metal ice oxides and alkaline earth metal alcoholates, the following general formula (2)
  • R is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent or a group which may have a substituent. (Represents a reel group)
  • the aldoxime represented by the formula is heated, and water generated as the reaction proceeds is distilled out of the reaction system.
  • the present invention is represented by the following reaction formula.
  • the present invention provides an alkali metal hydroxide, an alkali metal alcoholate, an alkaline earth metal hydroxide and a lithium earth metal alcoholate in the presence of at least one catalyst selected from the group consisting of:
  • the nitrile represented by the general formula (1) is produced by heating the aldoxime represented by the general formula (2) and distilling water generated as the reaction progresses out of the reaction system.
  • the group represented by R preferably has 3 to 20 carbon atoms.
  • specific examples of the alkyl group include a heptyl group, a nonyl group, a pendyl group, a lauryl group, a myristyl group and the like.
  • the alkenyl group may contain two or more double bonds. Specific examples thereof include a 2,6-dimethyl-1,5-diheptagenyl group and a 2,6-dimethyl-15-heptenyl group. Is mentioned.
  • specific examples of the aralkyl group include a 2-phenyl group and a 2-styryl group.
  • Specific examples of the aryl group include a phenyl group and a methyl group. And a phenyl group and a dimethylphenyl group.
  • examples of the substituent contained in these groups include a cyano group, a hydroxyl group, a carbonyl group, a nitro group, a carbonyloxy group, a carbonyl group, and a halogen atom.
  • the raw compound used in the present invention i.e., rhodoxime (2)
  • rhodoxime (2) can be obtained, for example, by reacting the corresponding aldehyde with an inorganic salt of hydroxylamine according to a conventional method.
  • the catalyst used in the reaction includes an alkali metal hydroxide, an alkali metal alcoholate, an alkali metal carbonate, an alkali metal bicarbonate, and an ice oxidation of an alkaline earth metal.
  • an alkali metal hydroxide an alkali metal alcoholate, an alkali metal carbonate, an alkali metal bicarbonate, and an ice oxidation of an alkaline earth metal.
  • One or two or more selected from the group consisting of an alkali metal, an alkaline earth metal carbonate, an alkaline earth metal carbonate, and an alkaline earth metal bicarbonate can be used as appropriate.
  • sodium propoxide, lithium butoxide, sodium carbonate, sodium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, etc. Can use more than species
  • hydroxides of alkali metal, alcohols of alkali metal, hydroxides of alkaline earth metal and alcoholates of alkaline earth metal are considered from the viewpoint of reaction yield. It is preferable to use sodium hydroxide, and more preferably, from the viewpoint of manufacturing economy, sodium hydroxide and hydroxide hydroxide.
  • these catalysts are preferably used in a total amount of 0.1 to 50% by weight, and particularly preferably 0.1 to 5% by weight, based on the starting compound, rhodoxime (2). If the amount of catalyst used is less than 0.1% by weight, the yield of nitrile decreases, and even if the amount of catalyst used exceeds 50% by weight, the effect is less than that within 50% by weight. Little improvement is gained.
  • the reaction temperature for obtaining nitril (1) from terdoxime (2) is preferably from 80 to 200.
  • a hand for distilling the elongation generated as the reaction progresses out of the reaction system! is not particularly limited, but, for example, means for azeotropic removal using a solvent capable of azeotroping with water, means for removing by distillation under reduced pressure and evaporating the reaction system, etc. No.
  • Examples of the solvent that can be azeotropic with water include benzene, toluene, xylene, chlorobenzene, heptane and the like.
  • aldoxime (2) is produced by supplying aldoxime (2) at a reaction temperature under reduced pressure in a mixed solution of a boiling point solvent and the catalyst.
  • a means for sequentially distilling ice is preferred.
  • the boiling point solvent include solvents having a boiling point higher than that of nitrile (1) as a reaction product, for example, liquid paraffin, alkylbenzene and the like.
  • the reaction for obtaining ditolyl (1) from aldoxime (2) is usually carried out under normal pressure if the above-mentioned azeotropic solvent is used to remove water by azeotropic distillation.
  • azeotropic solvent used to remove water by azeotropic distillation.
  • Heptanoxime 50 g
  • hydroxylated water (2 g) and toluene (2) were charged into a 200-milliliter four-liter flask equipped with a stirrer, a thermometer and a Dean-Stark dehydrator. While the mixture was azeotropically distilled together with the mixture, stirring was continued at 120 for 2 hours, followed by cooling to 30 to 40 :. Then, after neutralization with acetic acid, toluene was distilled off and distillation was carried out. As a fraction (910 g Hg), 36.8 g was obtained. I got Analysis of this fraction showed a purity of 98.7%, a yield of 83%, a conversion of 97% and a selectivity of 86.? %, It was found that heptanotritol was formed.
  • Example 1 A reaction was conducted in the same manner as in Example 1 except that 1 g of each of the compounds shown in Table 1 was used as the basic catalyst, and 50 g of the compound shown in Table 1 was used as the raw material aldoxime to produce nitrile.
  • Table 1 shows the nitrile, yield, tilling rate, and selectivity obtained in each example.
  • the production method of the present invention can provide a nitrile useful as a raw material for organic synthesis of a fragrance or a fragrance, a pharmaceutical, etc. in a high yield and extremely advantageously from a production economic viewpoint. It can be expected to be used extensively in such fields.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé de production d'un nitrile répondant à la formule générale (1): RC=N, dans laquelle R représente alkyle, alcényle, aralkyle ou aryle dont chacun est éventuellement substitué, la production de ce composé étant obtenue par le chauffage d'une aldoxime répondant à la formule générale (2): RCH=NOH, dans laquelle R a la même notation que ci-dessus, en présence d'au moins un catalyseur sélectionné parmi les hydroxydes et les alcoolats de métaux alcalins et de métaux alcalino-terreux, puis par l'évacuation par distillation à partir du système réactionnel de l'eau formée au cours de la réaction. Ce procédé permet de produire, avec un rendement élevé et un coût remarquablement réduit, des nitriles utilisés comme matériau de départ pour la synthèse organique des parfums, des médicaments et analogues.
PCT/JP1992/000928 1991-07-25 1992-07-21 Procede de production de nitrile Ceased WO1993002046A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE69206250T DE69206250T2 (de) 1991-07-25 1992-07-21 Verfahren zur herstellung von nitrilen.
EP92915837A EP0550762B1 (fr) 1991-07-25 1992-07-21 Procede de production de nitrile

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP18622791 1991-07-25
JP3/186227 1991-07-25

Publications (1)

Publication Number Publication Date
WO1993002046A1 true WO1993002046A1 (fr) 1993-02-04

Family

ID=16184586

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1992/000928 Ceased WO1993002046A1 (fr) 1991-07-25 1992-07-21 Procede de production de nitrile

Country Status (5)

Country Link
EP (1) EP0550762B1 (fr)
AT (1) ATE130599T1 (fr)
DE (1) DE69206250T2 (fr)
ES (1) ES2079877T3 (fr)
WO (1) WO1993002046A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5892092A (en) * 1997-09-04 1999-04-06 Basf Aktiengesellschaft Preparation of aliphatic, unsaturated nitriles
JP2010180142A (ja) * 2009-02-03 2010-08-19 Kuraray Co Ltd シクロヘキサンカルボニトリルの製造方法
WO2013176088A1 (fr) 2012-05-21 2013-11-28 高砂香料工業株式会社 Procédé de fabrication d'un nitrile

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5457222A (en) * 1991-07-25 1995-10-10 Kao Corporation Process for producing nitrile
EP0731086B1 (fr) * 1995-03-09 1999-04-28 Ciba SC Holding AG Procédé de préparation de nitriles aromatiques
US5763638A (en) * 1996-02-15 1998-06-09 Ciba Specialty Chemicals Corporation Preparation of aromatic nitriles
JP3561178B2 (ja) 1999-06-02 2004-09-02 花王株式会社 ニトリルの製造方法
DE102004029812A1 (de) 2004-06-19 2006-05-24 Clariant Gmbh Verfahren zur Herstellung von Nitrilen aus Aldehydoximen durch Umsetzung mit Alkylphosphonsäureanhydriden
EP3443950A1 (fr) 2014-07-30 2019-02-20 Symrise AG Composition de parfum
WO2021228352A1 (fr) 2020-05-11 2021-11-18 Symrise Ag Composition de parfum
WO2025153182A1 (fr) 2024-01-18 2025-07-24 Symrise Ag Mélanges de parfums comprenant des nitriles aromatiques

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5896053A (ja) * 1981-12-02 1983-06-07 Sumitomo Chem Co Ltd ニトリル類の製造法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5896053A (ja) * 1981-12-02 1983-06-07 Sumitomo Chem Co Ltd ニトリル類の製造法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 100, No. 1, Abstract No. 100(1) : 6009q, 1984 (Columbus, Ohio, US), A. ORAZIO et al., Synthesis, (9), 741-2, 1983. *
CHEMICAL ABSTRACTS, Vol. 105, No. 3, Abstract No. 105(3) : 24029d, 1986 (Columbus, Ohio, US), STENBERG JOHN R., Chem. Ind. (Dekker), 22 (Catal. Org. React.), 373-9, 1985. *
CHEMICAL ABSTRACTS, Vol. 109, No. 9, Abstract No. 109(9) : 72976q, 1988 (Columbus, Ohio, US), K. KIYOTOMI et al., Chem. Lett., (2), 285-6, 1988. *
CHEMICAL ABSTRACTS, Vol. 82, No. 7, Abstract No. 82(7) : 43035a, 1975 (Columbus, Ohio, US), ROGIC MILORAD M. et al., J. Org. Chem., 39(23), 3424-6, 1974. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5892092A (en) * 1997-09-04 1999-04-06 Basf Aktiengesellschaft Preparation of aliphatic, unsaturated nitriles
EP0902012A3 (fr) * 1997-09-04 2002-08-14 Basf Aktiengesellschaft Procédé pour lapréparation de nitriles aliphatiques, insaturés
JP2010180142A (ja) * 2009-02-03 2010-08-19 Kuraray Co Ltd シクロヘキサンカルボニトリルの製造方法
WO2013176088A1 (fr) 2012-05-21 2013-11-28 高砂香料工業株式会社 Procédé de fabrication d'un nitrile
US9233916B2 (en) 2012-05-21 2016-01-12 Takasago International Corporation Method for producing nitrile

Also Published As

Publication number Publication date
EP0550762A4 (fr) 1994-03-23
DE69206250D1 (de) 1996-01-04
EP0550762A1 (fr) 1993-07-14
ATE130599T1 (de) 1995-12-15
EP0550762B1 (fr) 1995-11-22
DE69206250T2 (de) 1996-05-02
ES2079877T3 (es) 1996-01-16

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